JP4780959B2 - Ethynylation method - Google Patents
Ethynylation method Download PDFInfo
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- JP4780959B2 JP4780959B2 JP2004530118A JP2004530118A JP4780959B2 JP 4780959 B2 JP4780959 B2 JP 4780959B2 JP 2004530118 A JP2004530118 A JP 2004530118A JP 2004530118 A JP2004530118 A JP 2004530118A JP 4780959 B2 JP4780959 B2 JP 4780959B2
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- carbonyl compound
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- alkali metal
- ammonia
- metal hydroxide
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- 238000000034 method Methods 0.000 title claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 25
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 24
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002576 ketones Chemical class 0.000 claims abstract description 22
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 21
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- UHEPJGULSIKKTP-UHFFFAOYSA-N sulcatone Chemical compound CC(C)=CCCC(C)=O UHEPJGULSIKKTP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- RBGLEUBCAJNCTR-UHFFFAOYSA-N 6,10-dimethylundecan-2-one Chemical compound CC(C)CCCC(C)CCCC(C)=O RBGLEUBCAJNCTR-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- OHEFFKYYKJVVOX-UHFFFAOYSA-N sulcatol Natural products CC(O)CCC=C(C)C OHEFFKYYKJVVOX-UHFFFAOYSA-N 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- WHWDWIHXSPCOKZ-UHFFFAOYSA-N hexahydrofarnesyl acetone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)=O WHWDWIHXSPCOKZ-UHFFFAOYSA-N 0.000 claims description 8
- SAXWRVSDVXCTEL-SOFGYWHQSA-N (e)-6-methyloct-5-en-2-one Chemical compound CC\C(C)=C\CCC(C)=O SAXWRVSDVXCTEL-SOFGYWHQSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 claims description 6
- -1 formaldehyde, aldehyde Chemical class 0.000 claims description 5
- WHWDWIHXSPCOKZ-SJORKVTESA-N 6,10,14-Trimethyl-2-pentadecanone Natural products CC(C)CCC[C@@H](C)CCC[C@H](C)CCCC(C)=O WHWDWIHXSPCOKZ-SJORKVTESA-N 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000001371 (5E)-3,5-dimethylocta-1,5,7-trien-3-ol Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 3
- 125000005356 cycloalkylalkenyl group Chemical group 0.000 claims description 3
- ZJIQIJIQBTVTDY-SREVYHEPSA-N dehydrolinalool Chemical group CC(=C)\C=C/CC(C)(O)C=C ZJIQIJIQBTVTDY-SREVYHEPSA-N 0.000 claims description 3
- DWJDEJZHYRTMRR-UHFFFAOYSA-N 2,2-dimethoxypropanal Chemical compound COC(C)(OC)C=O DWJDEJZHYRTMRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 abstract description 3
- 235000021466 carotenoid Nutrition 0.000 abstract description 2
- 150000001747 carotenoids Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229930003231 vitamin Natural products 0.000 abstract description 2
- 229940088594 vitamin Drugs 0.000 abstract description 2
- 235000013343 vitamin Nutrition 0.000 abstract description 2
- 239000011782 vitamin Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- MULUCORRSAVKOA-UHFFFAOYSA-N 3,7,11,15-tetramethylhexadec-1-yn-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)C#C MULUCORRSAVKOA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- OWRXWSVBJIIORE-UHFFFAOYSA-N 3,7,11-trimethyldodec-1-yn-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)(O)C#C OWRXWSVBJIIORE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YWTIDNZYLFTNQQ-UHFFFAOYSA-N Dehydrolinalool Chemical group CC(C)=CCCC(C)(O)C#C YWTIDNZYLFTNQQ-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- FDTGUDJKAXJXLL-UHFFFAOYSA-N acetylene Chemical compound C#C.C#C FDTGUDJKAXJXLL-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RFAZFSACZIVZDV-UHFFFAOYSA-N butan-2-one Chemical compound CCC(C)=O.CCC(C)=O RFAZFSACZIVZDV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
- C07C33/042—Acyclic alcohols with carbon-to-carbon triple bonds with only one triple bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Formation Of Insulating Films (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、エチニル化方法に関する。より具体的には、本発明は、アセチレン不飽和アルコール（acetylenically unsaturated alcohol）（プロパルギルアルコール又はその１−一置換又は１，１−二置換誘導体）の製造方法であって、ホルムアルデヒド、ホルムアルデヒド以外のアルデヒド、又はケトン（これらは、各々、本明細書中において、一般に「カルボニル化合物」と称する。）をアンモニア及び水酸化アルカリ金属の存在下でアセチレン（エチン）と反応させるが、ここで、水酸化アルカリ金属とカルボニル化合物とのモル比が１：２００未満である方法に関する。 The present invention relates to an ethynylation process. More specifically, the present invention relates to a method for producing acetylenically unsaturated alcohol (propargyl alcohol or a 1-monosubstituted or 1,1-disubstituted derivative thereof), which comprises formaldehyde and an aldehyde other than formaldehyde Or a ketone, each of which is generally referred to herein as a “carbonyl compound”, is reacted with acetylene (ethyne) in the presence of ammonia and an alkali metal hydroxide, wherein the alkali hydroxide It relates to a process wherein the molar ratio of metal to carbonyl compound is less than 1: 200.
反応生成物は、多くの有用な最終生成物の合成における中間体として、特にビタミン及びカロチノイドの分野で有用である。例えば、そのような有用な中間体の１つはデヒドロリナロールであり、それ自体はシトラールを介してβ−イオノン及びイソフィトールに変換することができるが、それら自体は、それぞれ、ビタミンＡ及びビタミンＥの既知出発材料である。 The reaction products are useful as intermediates in the synthesis of many useful end products, particularly in the fields of vitamins and carotenoids. For example, one such useful intermediate is dehydrolinalool, which can itself be converted to β-ionone and isophytol via citral, which are themselves vitamin A and vitamin E, respectively. Is a known starting material.
アンモニア及び水酸化アルカリ金属の存在下でケトンをアセチレンと反応させることによるアセチレン不飽和アルコールの製造は、例えばドイツのアウスレーゲシュリフト（German Auslegeschrift）（ＤＡＳ）１２３２５７３から知られる。この特許公開広報によれば、水酸化アルカリ金属とケトンとのモル比を１：１０〜１：２００として水酸化アルカリ金属の存在下、−４０℃〜＋４０℃の温度において、エチニル化反応を行うことができる。ＤＡＳ１２３２５７３で提供される技術的データから明らかであるように、水酸化アルカリ金属の相対量が減少した場合、エチニル化生成物の収率は減少する。 The production of acetylenically unsaturated alcohols by reacting a ketone with acetylene in the presence of ammonia and an alkali metal hydroxide is known, for example, from German Auslegeschrift (DAS) 1232573 in Germany. According to this patent publication, the ethynylation reaction is carried out at a temperature of −40 ° C. to + 40 ° C. in the presence of an alkali metal hydroxide with a molar ratio of alkali metal hydroxide to ketone of 1:10 to 1: 200. be able to. As is apparent from the technical data provided in DAS1232573, the yield of ethynylated product decreases when the relative amount of alkali metal hydroxide is reduced.
驚いたことに、水酸化アルカリ金属とカルボニル化合物とのモル比が１：２００未満である場合、すなわち該比が１：＞２００である場合、アンモニア及び水酸化アルカリ金属の存在下で適切なカルボニル化合物をアセチレンと反応させることにより、短い反応時間内に優れた収率でアセチレン不飽和アルコールを得ることができることが今や見出された。そのような少量の水酸化アルカリ金属、すなわち、ＤＡＳ１２３２５７３の技術に従って用いることができる量よりも非常に少ない相対量の使用により、不要な副産物として処分される塩の量を減少するのみならず、驚いたことにジオール副産物の形成をも減少させる結果となる。従前に知られたケトンアセチル化では、温度が上がるにつれてジオール副産物の形成が増加する傾向にあるので、本発明による反応を、ジオール副産物の形成を低いレベルでなお維持しながら、より高温で、すなわち、冷却することなく行うことができる。 Surprisingly, when the molar ratio of alkali metal hydroxide to carbonyl compound is less than 1: 200, ie when the ratio is 1:> 200, an appropriate carbonyl in the presence of ammonia and alkali metal hydroxide. It has now been found that by reacting a compound with acetylene, an acetylenically unsaturated alcohol can be obtained in excellent yield within a short reaction time. The use of such a small amount of alkali metal hydroxide, i.e. much less than that which can be used according to the technology of DAS1232573, not only reduces the amount of salt disposed as an unwanted by-product, but is also surprising. This also reduces the formation of diol by-products. Since the previously known ketone acetylation tends to increase the formation of diol by-products with increasing temperature, the reaction according to the present invention can be carried out at higher temperatures, i.e. while still maintaining the diol by-product formation at a low level. Can be done without cooling.
したがって、本発明は、ホルムアルデヒド、アルデヒド、又はケトン（カルボニル化合物）をアンモニア及び水酸化アルカリ金属の存在下でアセチレンと反応させることを含むアセチレン不飽和アルコールの製造方法であって、水酸化アルカリ金属とカルボニル化合物とのモル比が１：２００未満であることを特徴とする方法を提供する。 Accordingly, the present invention is a process for producing an acetylenically unsaturated alcohol comprising reacting formaldehyde, aldehyde, or ketone (carbonyl compound) with acetylene in the presence of ammonia and an alkali metal hydroxide, A method is provided wherein the molar ratio to the carbonyl compound is less than 1: 200.
本発明の方法に従ってアセチレンと反応することができる最も単純なカルボニル化合物は、ホルムアルデヒド（ＨＣＨＯ）であり、生成物はプロパルギルアルコール（ＨＣ≡ＣＣＨ２ＯＨ）である。 The simplest carbonyl compound that can react with acetylene according to the method of the present invention is formaldehyde (HCHO) and the product is propargyl alcohol (HC≡CCH 2 OH).
本発明の方法に従ってアセチレと反応することができる他の任意のアルデヒド又はケトンの性質は極めて重要というわけではないが、アセチレンと反応してアセチレン不飽和アルコールを形成することが知られている、すなわち、以下の式に従う任意のアルデヒド又はケトンを用いることができる。 The nature of any other aldehyde or ketone that can react with acetyles according to the method of the present invention is not critical, but is known to react with acetylenes to form acetylenically unsaturated alcohols, ie Any aldehyde or ketone according to the following formula can be used.
ここで、点線によって「中心」炭素原子に結合している不特定の部分は、既知のアルデヒド及びケトンあるいは他の任意のアルデヒド及びケトンにあるものであり、これらは既知のものと同様にして製造することができる。したがって、例えば、ホルムアルデヒドなどのアルデヒド、又はケトンは、ドイツのオッフェンレーグングスシュリフト（German Offenlegungsschrift）（ＤＯＳ）２０１８９７１（その内容を参照目的のため本明細書中に取り入れる。）で定義されている式「Ｒ５−ＣＯ−Ｒ６」で示されるアルデヒド又はケトンのうちの１つであってもよい。好ましくは、出発カルボニル化合物は、以下の一般式で示されるケトンである。
Ｒ１−ＣＨ２−ＣＯ−ＣＨ２−Ｒ２ Ｉ
（式中、Ｒ１及びＲ２の各々は、独立して、水素、アルキル、アルケニル、シクロアルキル−アルキル、シクロアルキル−アルケニル、シクロアルケニル−アルキル、又はシクロアルケニル−アルケニルを意味し、言及した基の最後の４つは、各々、必要に応じてそのシクロアルキル環又はシクロアルケニル環上において１〜３個のメチル基又はエチル基により場合により置換されており、−ＣＨ２−ＣＯ−ＣＨ２−部分の炭素原子を含む炭素原子の合計数が４０個を上回らない。）
Here, the unspecified part bonded to the “center” carbon atom by the dotted line is in a known aldehyde and ketone or any other aldehyde and ketone, which are prepared in the same manner as known ones. can do. Thus, for example, aldehydes such as formaldehyde or ketones are defined in German Offenlegungsschrift (DOS) 2010971, the contents of which are incorporated herein for reference purposes. It may be one of an aldehyde or a ketone represented by the formula “R 5 —CO—R 6 ”. Preferably, the starting carbonyl compound is a ketone having the general formula:
R 1 —CH 2 —CO—CH 2 —R 2 I
In which each of R 1 and R 2 independently represents hydrogen, alkyl, alkenyl, cycloalkyl-alkyl, cycloalkyl-alkenyl, cycloalkenyl-alkyl, or cycloalkenyl-alkenyl the last four of each are optionally substituted by one to three methyl or ethyl groups on the cycloalkyl ring or cycloalkenyl ring optionally, -CH 2 -CO-CH 2 - (The total number of carbon atoms, including partial carbon atoms, does not exceed 40.)
一般式Ｉで示されるケトンの上記定義において、Ｒ１及び／又はＲ２が意味するアルキル基は、好適には、最高で２２個の炭素原子を含有し、かつ直鎖又は分枝であってもよく、このことはアルケニル基にも適用される。さらに、該アルケニル基は、最高で４個の二重結合を特徴としてもよい。Ｒ１及び／又はＲ２が意味するシクロアルキル−アルキル、シクロアルケニル−アルキル、シクロアルキル−アルケニル、又はシクロアルケニル−アルケニル基は、必要に応じて、５〜１２の環員を有するシクロアルキル又はシクロアルケニル環を特徴とし；そのような基のアルキル又はアルケニル部分は１〜８個の炭素原子を含有し、かつ、直鎖又は分枝であることができ、またそのような基の一部がアルケニルの場合には該アルケニル部分は最高で４つの二重結合を特徴とすることもできる。さらに、式Ｉの定義でも示している通り、このような基のシクロアルキル又はシクロアルケニルの環部分は、非置換であるか、あるいは１個、２個又は３個のメチル基又はエチル基により置換され、それにより二置換又は三置換の場合には置換基は同じ（メチル又はエチル）あるいは異なる（メチル置換基及びエチル置換基の混合）ことができる。場合により置換される特に好ましい（シクロアルケニル−アルキル又はシクロアルケニル−アルケニルの一部としての）シクロアルケニル基は、周知の２，６，６−トリメチル−１−シクロヘキセン−１−イル基である。 In the above definition of the ketone of the general formula I, the alkyl radicals represented by R 1 and / or R 2 preferably contain up to 22 carbon atoms and are straight-chain or branched. This also applies to alkenyl groups. Furthermore, the alkenyl group may be characterized by up to 4 double bonds. The cycloalkyl-alkyl, cycloalkenyl-alkyl, cycloalkyl-alkenyl, or cycloalkenyl-alkenyl group represented by R 1 and / or R 2 is optionally substituted with cycloalkyl or cyclohexane having 5 to 12 ring members. Characterized by an alkenyl ring; the alkyl or alkenyl part of such a group contains from 1 to 8 carbon atoms and may be straight-chain or branched, and a part of such a group may be alkenyl In this case, the alkenyl moiety can also be characterized by up to four double bonds. Furthermore, as also indicated in the definition of formula I, the cycloalkyl or cycloalkenyl ring part of such a group is unsubstituted or substituted by 1, 2 or 3 methyl or ethyl groups. Thus, in the case of di- or tri-substitution, the substituents can be the same (methyl or ethyl) or different (mixture of methyl and ethyl substituents). A particularly preferred cycloalkenyl group (as part of cycloalkenyl-alkyl or cycloalkenyl-alkenyl) optionally substituted is the well-known 2,6,6-trimethyl-1-cyclohexen-1-yl group.
適切な場合に、任意の環メチル置換基又は環エチル置換基を含む、Ｒ１又はＲ２いずれかの炭素原子合計数は、全体として最高で４０個の炭素原子を含有するＲ１−ＣＨ２−ＣＯ−ＣＨ２−Ｒ２分子の基準を満たすため、明らかに、それぞれ残りのＲ２又はＲ１の炭素原子合計数により制限される。 Where appropriate, the total number of carbon atoms in either R 1 or R 2 , including any ring methyl substituent or ring ethyl substituent, is R 1 —CH 2 containing a total of up to 40 carbon atoms. In order to meet the criteria for —CO—CH 2 —R 2 molecules, it is clearly limited by the total number of carbon atoms in the remaining R 2 or R 1 respectively.
本発明の方法は、メチルエチルケトン（２−ブタノン）、６−メチル−５−ヘプテン−２−オン、６−メチル−５−オクテン−２−オン、６，１０−ジメチル−２−ウンデカノン（ヘキサヒドロプソイドイオノン）、４−（２，６，６−トリメチル−１−シクロヘキセン−ｌ−イル）−３−ブテン−２−オン、及び６，１０，１４−トリメチル−２−ペンタデカノン（式Ｉで示されるすべてのケトン）のエチニル化に適用される場合、さらに式Ｉで示されるケトンではないが、それにもかかわらず、本発明の方法に従ってアセチレンと反応することができるその他多数ある中のケトンの１つであるメチルグリオキサルジメチルアセタール［ＣＨ３ＣＯＣＨ（ＯＣＨ３）２］のエチニル化に適用される場合に、特に興味深い。これらの具体的に命名されたケトンの中で、６−メチル−５−ヘプテン−２−オンは本発明の方法によってアセチレンと反応することができる特に好ましいケトンであり、この場合の生成物は３，７−ジメチル−６−オクテン−１−イン−３−オール（デヒドロリナロール）である。 The process of the present invention comprises methyl ethyl ketone (2-butanone), 6-methyl-5-hepten-2-one, 6-methyl-5-octen-2-one, 6,10-dimethyl-2-undecanone (hexahydropone). Soidionone), 4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -3-buten-2-one, and 6,10,14-trimethyl-2-pentadecanone (shown in Formula I) Is one of the many other ketones that are not the ketones of formula I but nevertheless can be reacted with acetylene according to the process of the present invention. It is of particular interest when applied to the ethynylation of the methylglyoxal dimethyl acetal [CH 3 COCH (OCH 3 ) 2 ]. Among these specifically named ketones, 6-methyl-5-hepten-2-one is a particularly preferred ketone that can be reacted with acetylene by the process of the present invention, in which the product is 3 , 7-dimethyl-6-octen-1-in-3-ol (dehydrolinalool).
本発明の方法で塩基性触媒として用いられる水酸化アルカリ金属として、水酸化ナトリウム又は水酸化カリウムを用いてもよく、このうち後者を用いることが好ましい。 Sodium hydroxide or potassium hydroxide may be used as the alkali metal hydroxide used as the basic catalyst in the method of the present invention, and the latter is preferably used.
本発明の方法で溶媒として用いられるアンモニアを、温度及び圧力を適切に選択することによって液状で維持し、それによって、同時に反応容器中に十分なアセチレン圧力もまた付与され、維持されなければならない。反応温度は、約０℃〜約４０℃の範囲であることが好都合である。圧力は、反応温度に依存して適切な値で維持され、約５ｂａｒ〜約２０ｂａｒ（約０．５ＭＰａ〜約２ＭＰａ）が好適である。反応溶媒として液化アンモニアを用いることにより、本発明の方法は有機溶媒の使用を回避しており、このことは本発明の方法の有利な点の１つである。 Ammonia used as a solvent in the process of the present invention must be maintained in liquid form by appropriate selection of temperature and pressure, so that sufficient acetylene pressure must also be applied and maintained in the reaction vessel at the same time. The reaction temperature is conveniently in the range of about 0 ° C to about 40 ° C. The pressure is maintained at a suitable value depending on the reaction temperature, and is preferably about 5 bar to about 20 bar (about 0.5 MPa to about 2 MPa). By using liquefied ammonia as the reaction solvent, the process of the present invention avoids the use of organic solvents, which is one of the advantages of the process of the present invention.
エチニル化は、ほぼ室温（約２０℃）〜約３５℃の温度で行うことが好ましい。 The ethynylation is preferably performed at a temperature of about room temperature (about 20 ° C.) to about 35 ° C.
本発明の方法を行うための反応混合物中におけるアセチレンとホルムアルデヒド、アルデヒド、又はケトン（カルボニル化合物）、例えば式Ｉで示されるケトンとのモル比は、一般に、約２：１〜約６：１である。さらに、上記方法におけるアンモニアとカルボニル化合物とのモル比は、約８：１〜約３５：１であり、好ましくは約１０：１〜約３０：１である。 The molar ratio of acetylene to formaldehyde, aldehyde, or ketone (carbonyl compound), for example a ketone of formula I, in the reaction mixture for carrying out the process of the invention is generally from about 2: 1 to about 6: 1. is there. Further, the molar ratio of ammonia to carbonyl compound in the above process is from about 8: 1 to about 35: 1, preferably from about 10: 1 to about 30: 1.
本発明の方法の特徴は、触媒として用いられる比較的に非常に少ない量の水酸化アルカリ金属であり、すなわち、水酸化アルカリ金属とカルボニル化合物とのモル比が１：２００未満（１：＞２００）である。本発明の方法を行うモル範囲は、約１：５００〜１：２００が都合よく、約１：３００〜約１：２２０が好ましい。 A feature of the process of the invention is the relatively very small amount of alkali metal hydroxide used as a catalyst, i.e. the molar ratio of alkali metal hydroxide to carbonyl compound is less than 1: 200 (1:> 200). ). The molar range for carrying out the process of the present invention is conveniently about 1: 500 to 1: 200, preferably about 1: 300 to about 1: 220.
カルボニル化合物のエチニル化のためにそれ自体で知られた方式で本発明の方法を行うことができる。典型的には、バッチ式操作について、所望の量の水酸化アルカリ金属水溶液、カルボニル化合物、及びアセチレンを反応器中に入れる。次いで、反応器を密封し、アンモニアを繰り返し充填し通気することにより不活性化させる。最後に、所望の量のアンモニアを反応器に入れる。次いで、アセチレンも所望の量で攪拌しながら添加して、反応を開始する。反応中に、一定のケトン：アセチレンモル比を維持するために、さらにアセチレンを半継続的に添加してもよい。 The process according to the invention can be carried out in a manner known per se for the ethynylation of carbonyl compounds. Typically, for batch operations, the desired amount of aqueous alkali metal hydroxide, carbonyl compound, and acetylene are placed in the reactor. The reactor is then sealed and deactivated by repeatedly filling and venting with ammonia. Finally, the desired amount of ammonia is placed in the reactor. Acetylene is then added in the desired amount with stirring to initiate the reaction. Additional acetylene may be added semi-continuously during the reaction to maintain a constant ketone: acetylene molar ratio.
あるいは、例えば、アセチレン及びアンモニアの混合物をカルボニル化合物及び水酸化アルカリ水溶液と一緒に反応器（例えば、ピストン型反応器）中に継続的に添加し、そして生成物を継続的に回収することにより、本発明による方法を継続的に行うことができる。本発明の方法は、継続的な方式で行うことが好ましい。 Alternatively, for example, by continuously adding a mixture of acetylene and ammonia together with a carbonyl compound and an aqueous alkali hydroxide solution into a reactor (eg, a piston-type reactor) and continuously recovering the product, The method according to the invention can be carried out continuously. The method of the present invention is preferably performed in a continuous manner.
以下の実施例は、本発明の方法を例示するものである。 The following examples illustrate the method of the present invention.
実施例１
３，７−ジメチル−６−オクテン−１−イン−オールを製造するための６−メチル−５−ヘプテン−２−オンのエチニル化
４５％（ｗｔ．／ｖｏｌ．）水溶液中の水酸化カリウム（ＫＯＨ）７９６ｍｇ及び６−メチル−５−ヘプテン−２−オン（ＭＨ）１９４．５ｇを反応器中に入れた；したがってＫＯＨ：ＭＨのモル比は１：２５０であった。反応器から４倍の空気を排気し、続いて窒素でフラッシュした（反応器の不活性化）後、アンモニア３６９ｇを入れた。次いで、アンモニア及びアセチレンの混合物中２１％（ｗｔ．／ｖｏｌ．）のアセチレンに相当するアセチレンを添加し、３０℃で１６．１ｂａｒ（１．６１ＭＰａ）の圧力を付与した。反応器の内容物をガス攪拌により攪拌した。ガスクロマトグラフィー（ＧＣ）による内容物の分析のため、試料を種々の時間間隔で採取した。主な量の所望の生成物である３，７−ジメチル−６−オクテン−１−イン−３−オール（デヒドロリナロール；ＤＬＬ）並びにほんの少量のジオール副産物及び無変化のＭＨが存在していることを確証したため、５時間後に反応を最終的に終了した。結果を以下の表１に提示する。
Example 1
Ethynylation of 6-methyl-5-hepten-2-one to produce 3,7-dimethyl-6-octen-1-in-ol Potassium hydroxide in 45% (wt./vol.) Aqueous solution ( 796 mg (KOH) and 194.5 g 6-methyl-5-hepten-2-one (MH) were placed in the reactor; thus the molar ratio of KOH: MH was 1: 250. After evacuating the reactor 4 times air and subsequently flushing with nitrogen (reactor deactivation), 369 g of ammonia was added. Then, acetylene corresponding to 21% (wt./vol.) Acetylene in a mixture of ammonia and acetylene was added and a pressure of 16.1 bar (1.61 MPa) was applied at 30 ° C. The reactor contents were stirred by gas stirring. Samples were taken at various time intervals for analysis of the contents by gas chromatography (GC). The main amount of desired product 3,7-dimethyl-6-octen-1-in-3-ol (dehydrolinalol; DLL) and only a small amount of diol by-product and unchanged MH are present. The reaction was finally terminated after 5 hours. The results are presented in Table 1 below.
表１：時間に対する生成物の組成［分（ｍｉｎ．）／時（ｈｒ．又はｈｒｓ．）］
実施例２
３，７，１１−トリメチル−１−ドデシン−３−オールを製造するための６，１０−ジメチル−２−ウンデカノンのエチニル化
実施例１と同様に、４５％（ｗｔ．／ｖｏｌ．）水溶液中の水酸化カリウム３８７ｍｇ、６，１０−ジメチル−２−ウンデカノン（ヘキサヒドロプソイドイオノン；ＨＰＩ）１５３．８ｇ、アンモニア３６０ｇ、及びアセチレンを１６．３ｂａｒ（１．６３ＭＰａ）で３０℃において反応させた；したがって、ＫＯＨ：ＨＰＩのモル比は１：２５０であった。５時間後、主な量の所望の生成物である３，７，１１−トリメチル−１−ドデシン−３−オール（Ｃ１５−アセチレン性アルコール；Ｃ１５−ＡＡ）並びにほんの少量のジオール副産物及び無変化のＨＰＩが存在していることをＧＣにより確証した。結果を以下の表２に提示する。
Example 2
Ethynylation of 6,10-dimethyl-2-undecanone to produce 3,7,11-trimethyl-1-dodecin-3-ol Similar to Example 1, in 45% (wt./vol.) Aqueous solution 387 mg of potassium hydroxide, 153.8 g of 6,10-dimethyl-2-undecanone (hexahydropseudoionone; HPI), 360 g of ammonia, and acetylene were reacted at 16.3 bar (1.63 MPa) at 30 ° C. Therefore the molar ratio of KOH: HPI was 1: 250. After 5 hours, the desired product of major amounts 3,7,11-trimethyl-1-dodecyn-3-ol (C 15 - acetylenic alcohols; C 15 -AA) and only small amounts of diol by-products and free The presence of altered HPI was confirmed by GC. The results are presented in Table 2 below.
表２：時間に対する生成物の組成
実施例３
３，７，１１，１５−テトラメチル−１−ヘキサデシン−３−オールを製造するための６，１０，１４−トリメチル−２−ペンタデカノンのエチニル化
実施例１と同様に、４５％（ｗｔ．／ｖｏｌ．）水溶液中の水酸化カリウム３５８ｍｇ、６，１０，１４−トリメチル−２−ペンタデカノン（Ｃ１８−ケトン）１９２．３ｇ、アンモニア３５１ｇ、及びアセチレンを１６．８ｂａｒ（１．６８ＭＰａ）で３０℃において反応させた；したがって、ＫＯＨ：Ｃ１８−ケトンのモル比は１：２５０であった。５時間後、主な量の所望の生成物である３，７，１１，１５−テトラメチル−１−ヘキサデシン−３−オール（デヒドロイソフィトール；ＤＩＰ）並びにほんの少量のジオール副産物及び無変化のＣ１８−ケトンが存在していることをＧＣにより確証した。結果を以下の表３に提示する。
Example 3
Ethynylation of 6,10,14-trimethyl-2-pentadecanone to produce 3,7,11,15-tetramethyl-1-hexadecin-3-ol 45% (wt./wt) as in Example 1. vol.) 358 mg of potassium hydroxide in aqueous solution, 192.3 g of 6,10,14-trimethyl-2-pentadecanone (C 18 -ketone), 351 g of ammonia, and acetylene at 16.8 bar (1.68 MPa) at 30 ° C. The molar ratio of KOH: C 18 -ketone was thus 1: 250. After 5 hours, the main amount of desired product 3,7,11,15-tetramethyl-1-hexadecin-3-ol (dehydroisophytol; DIP) and only a small amount of diol by-product and unchanged C The presence of 18 -ketone was confirmed by GC. The results are presented in Table 3 below.
表３：時間に対する生成物の組成
実施例４
３，７−ジメチル−６−ノネン−１−イン−３−オールを製造するための６−メチル−５−オクテン−２−オンのエチニル化
実施例１と同様に、４５％（ｗｔ．／ｖｏｌ．）水溶液中の水酸化カリウム５９３ｍｇ、６−メチル−５−オクテン−２−オン（ＭＯ）１６６．８ｇ、アンモニア３８１ｇ、及びアセチレンを１６．１ｂａｒ（１．６１ＭＰａ）で３０℃において反応させた；したがって、ＫＯＨ：ＭＯのモル比は１：２５０であった。５時間後、主な量の所望の生成物である３，７−ジメチル−６−ノネン−１−イン−３−オール（「エチルデヒドロリナロール」；ＥＤＬＬ）並びにほんの少量のジオール副産物及び無変化のＭＯが存在していることをＧＣにより確証した。結果を以下の表４に提示する。
Example 4
Ethynylation of 6-methyl-5-octen-2-one to produce 3,7-dimethyl-6-nonen-1-in-3-ol 45% (wt./vol) as in Example 1. .) 593 mg potassium hydroxide, 166.8 g 6-methyl-5-octen-2-one (MO), 381 g ammonia, and acetylene in aqueous solution were reacted at 30 ° C. at 16.1 bar (1.61 MPa); Therefore, the KOH: MO molar ratio was 1: 250. After 5 hours, the main amount of the desired product, 3,7-dimethyl-6-nonen-1-in-3-ol (“ethyl dehydrolinalol”; EDLL) and only a small amount of diol by-product and unchanged The presence of MO was confirmed by GC. The results are presented in Table 4 below.
表４：時間に対する生成物の組成
実施例５
２−エチル−３−ブチン−２−オールを製造するためのメチルエチルケトンのエチニル化
実施例１と同様に、４５％（ｗｔ．／ｖｏｌ．）の水溶液中の水酸化カリウム７４０ｍｇ、メチルエチルケトン（ＭＥＫ）１５３．７ｇ、アンモニア３８８ｇ、及びアセチレンを１６．０ｂａｒ（１．６０ＭＰａ）で３０℃において反応させた；したがって、ＫＯＨ：ＭＥＫのモル比は１：３５９であった。既に１時間後、主な量の所望の生成物である２−エチル−３−ブチン−２−オール（ＥＢ）並びにほんの少量のジオール副産物及び無変化のＭＥＫが存在していることをＧＣにより確証した。結果を以下の表５に提示する。
Example 5
Ethynylation of methyl ethyl ketone to produce 2-ethyl-3-butyn-2-ol As in Example 1, 740 mg potassium hydroxide in a 45% (wt./vol.) Aqueous solution, methyl ethyl ketone (MEK) 153 0.7 g, 388 g ammonia, and acetylene were reacted at 16.0 bar (1.60 MPa) at 30 ° C .; thus the molar ratio of KOH: MEK was 1: 359. Already after 1 hour, GC confirms the presence of the main amount of desired product 2-ethyl-3-butyn-2-ol (EB) and only a small amount of diol by-product and unchanged MEK. did. The results are presented in Table 5 below.
表５：時間に対する生成物の組成
Claims (11)
Ｒ１−ＣＨ２−ＣＯ−ＣＨ２−Ｒ２ Ｉ
（式中、Ｒ１及びＲ２の各々が、独立して、水素、アルキル、アルケニル、シクロアルキル−アルキル、シクロアルキル−アルケニル、シクロアルケニル−アルキル、又はシクロアルケニル−アルケニルを意味し、言及した基の最後の４つは、各々、必要に応じて、そのシクロアルキル環又はシクロアルケニル環上において１〜３個のメチル基又はエチル基により場合により置換されており、−ＣＨ２−ＣＯ−ＣＨ２−部分の炭素原子を含む炭素原子の合計数が４０個を上回らない）で示されるケトンである請求項１又は２に記載の方法。The carbonyl compound is represented by the general formula I:
R 1 —CH 2 —CO—CH 2 —R 2 I
In which each of R 1 and R 2 independently represents hydrogen, alkyl, alkenyl, cycloalkyl-alkyl, cycloalkyl-alkenyl, cycloalkenyl-alkyl, or cycloalkenyl-alkenyl. the last four are each optionally its being optionally substituted by one to three methyl or ethyl groups on the cycloalkyl ring or cycloalkenyl ring, -CH 2 -CO-CH 2 The method according to claim 1, wherein the total number of carbon atoms including the carbon atoms of the moiety is not more than 40).
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| JP (1) | JP4780959B2 (en) |
| KR (1) | KR20050056986A (en) |
| CN (1) | CN1286789C (en) |
| AT (1) | ATE413370T1 (en) |
| AU (1) | AU2003255407A1 (en) |
| DE (1) | DE60324564D1 (en) |
| RU (1) | RU2323201C2 (en) |
| WO (1) | WO2004018400A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101277918B (en) * | 2005-09-29 | 2012-11-14 | 帝斯曼知识产权资产管理有限公司 | Cleavage of alkynediols |
| EP1963246B1 (en) * | 2005-12-20 | 2017-08-23 | DSM IP Assets B.V. | Process for ubiquinone intermediates |
| ATE421496T1 (en) | 2006-04-25 | 2009-02-15 | Dsm Ip Assets Bv | TRANSPORT OF ETHINE IN THE FORM OF AN ALPHA-ALKYNOL AS AN ETHINE PRECURSOR |
| KR100915390B1 (en) * | 2008-05-02 | 2009-09-03 | 한국해양연구원 | Composition comprising novel acetylenic alcohol compound or the extract of reniochalina sp. for preventing and treating cancer |
| CN102476978B (en) * | 2010-11-24 | 2015-04-08 | 杨朝辉 | Novel synthetic method preparing alkynol compound from acetylene |
| CN103113188A (en) * | 2011-11-17 | 2013-05-22 | 河北百灵威超精细材料有限公司 | Novel low-cost synthesis method of alkynol compounds |
| US20150307439A1 (en) | 2012-10-08 | 2015-10-29 | Dsm Ip Assets B.V. | Flavor and fragrance formulation (i) |
| CN104854072A (en) | 2012-12-18 | 2015-08-19 | 帝斯曼知识产权资产管理有限公司 | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 6,10-dimetylundeca-3,5,9-trien-2-one |
| WO2014096098A1 (en) | 2012-12-18 | 2014-06-26 | Dsm Ip Assets B.V. | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 6,10,14-trimetylpentadeca-5,9,13-trien-2-one or 6,10,14-trimetylpentadeca-5,9-dien-2-one |
| WO2014096067A1 (en) | 2012-12-18 | 2014-06-26 | Dsm Ip Assets B.V. | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from (r)-6,10,14-trimetylpentadec-5-en-2-one |
| EA027932B1 (en) * | 2013-01-23 | 2017-09-29 | ДСМ АйПи АССЕТС Б.В. | Process for the production of 2-alkyl-3-butyn-2-ols |
| MX2015011881A (en) | 2013-03-13 | 2016-01-25 | Dsm Ip Assets Bv | Process for the preparation of 3,7-dimethylnonan-1-ol. |
| WO2016059151A1 (en) * | 2014-10-16 | 2016-04-21 | Dsm Ip Assets B.V. | Ethynylation of polyunsaturated aldehydes and ketones |
| US11078178B2 (en) | 2017-09-04 | 2021-08-03 | Dsm Ip Assets B.V. | 6-chromanol derivatives and their synthesis |
| CN108358749B (en) * | 2018-02-07 | 2021-06-22 | 重庆弛源化工有限公司 | Method for producing propargyl alcohol |
| EP3640233A1 (en) | 2018-10-16 | 2020-04-22 | Basf Se | Ethers and esters of tertiary alkanols for use as aroma chemicals |
| EP3640234A1 (en) | 2018-10-16 | 2020-04-22 | Basf Se | Ethers and esters of 1-substituted cycloalkanols for use as aroma chemicals |
| CN110143849B (en) * | 2019-06-05 | 2020-01-10 | 山东新和成维生素有限公司 | Preparation method of alkynol |
| CN113880691B (en) * | 2021-09-27 | 2023-09-01 | 四川众邦新材料股份有限公司 | Method for synthesizing trimethyl dodecanol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000517326A (en) * | 1996-09-03 | 2000-12-26 | ビーエーエスエフ アクチェンゲゼルシャフト | Process for producing alkyne diol or a mixture of alkyne diol and alkyne monool |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3283014A (en) * | 1966-11-01 | Acetylenic alcohols from ketones and acetylene using aqueous alkaline hy- droxide catalyst | ||
| US3082260A (en) * | 1959-05-20 | 1963-03-19 | Air Reduction | Preparation of acetylenic alcohols |
| US3383427A (en) * | 1962-12-17 | 1968-05-14 | Dow Chemical Co | Procedure for synthesis of propargyl alcohol |
| US3709946A (en) * | 1970-07-31 | 1973-01-09 | Air Prod & Chem | Preparation of acetylenic alcohols |
| FR2236822A1 (en) * | 1973-07-09 | 1975-02-07 | Inst Orch Khim | Tertiary acetylenic alcohols prodn - by reacting ketones with acetylene in liquid ammonia in the presence of alkai catalysts |
| DE10123066A1 (en) | 2001-05-11 | 2002-11-14 | Basf Ag | Process for the production of higher alpha, beta-unsaturated alcohols |
| DE102004009311A1 (en) * | 2004-02-26 | 2005-09-08 | Basf Ag | Process for the preparation of a propargyl alcohol and an allyl alcohol |
-
2003
- 2003-08-09 DE DE60324564T patent/DE60324564D1/en not_active Expired - Lifetime
- 2003-08-09 KR KR1020057002556A patent/KR20050056986A/en not_active Application Discontinuation
- 2003-08-09 AT AT03792289T patent/ATE413370T1/en not_active IP Right Cessation
- 2003-08-09 EP EP03792289A patent/EP1532092B1/en not_active Expired - Lifetime
- 2003-08-09 CN CNB038189887A patent/CN1286789C/en not_active Expired - Lifetime
- 2003-08-09 RU RU2005107412/04A patent/RU2323201C2/en active
- 2003-08-09 JP JP2004530118A patent/JP4780959B2/en not_active Expired - Lifetime
- 2003-08-09 US US10/524,762 patent/US7638658B2/en not_active Expired - Lifetime
- 2003-08-09 WO PCT/EP2003/008867 patent/WO2004018400A1/en active Application Filing
- 2003-08-09 AU AU2003255407A patent/AU2003255407A1/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000517326A (en) * | 1996-09-03 | 2000-12-26 | ビーエーエスエフ アクチェンゲゼルシャフト | Process for producing alkyne diol or a mixture of alkyne diol and alkyne monool |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050240066A1 (en) | 2005-10-27 |
| ATE413370T1 (en) | 2008-11-15 |
| JP2005538142A (en) | 2005-12-15 |
| RU2323201C2 (en) | 2008-04-27 |
| US7638658B2 (en) | 2009-12-29 |
| AU2003255407A1 (en) | 2004-03-11 |
| CN1286789C (en) | 2006-11-29 |
| DE60324564D1 (en) | 2008-12-18 |
| KR20050056986A (en) | 2005-06-16 |
| EP1532092B1 (en) | 2008-11-05 |
| EP1532092A1 (en) | 2005-05-25 |
| RU2005107412A (en) | 2006-01-27 |
| WO2004018400A1 (en) | 2004-03-04 |
| CN1675152A (en) | 2005-09-28 |
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